The recent observation of ferroelectricity in ultra thin films of hafnium oxide (HfO₂) has been attributed to the orthorhombic (o) phase of HfO₂ with space group Pca2₁. Although this oxide is polymorphic in nature, this polar o-phase is known to be stabilized in the doped thin film oxide. The objective of the present experiment is to stabilize the o-phases in La doped bulk polycrystalline HfO₂ and investigate their evolution with the doping concentration through Time Differential Perturbed Angular Correlation (TDPAC), X-ray Absorption Near Edge Structure (XANES) and Extended X-ray Absorption Fine Structure (EXAFS) measurements. The present work reports the presence of both the polar Pca2₁ phase and the antipolar Pbca phase at different La-concentrations. Two o-phases of HfO₂ with space groups Pca2₁ and Pbca, difficult to distinguish by other complimentary methods, could be unambiguously identified by utilizing the atomic scale sensitivity of the electric field gradient (EFG) embedded in TDPAC spectroscopy. The determination of the oxidation state and the local environment of La-atoms by XANES and EXAFS measurements illuminates the microscopic role of the dopant in stabilizing the o-phase. The ‘‘solute drag model’’ proposes a critical crystallite size for the nucleation of the o-phase in bulk HfO₂ and explains the role of the La-dopant in stabilizing the o-phase. Thus the present study shows the possibility of stabilizing the polar o-phase and hence attaining ferroelectricity in bulk HfO₂ to augment the scope of future application for this ferroelectric device.